CN102015815B - Polyisocyanate composition and two-package type coating composition using same - Google Patents
Polyisocyanate composition and two-package type coating composition using same Download PDFInfo
- Publication number
- CN102015815B CN102015815B CN200980114114.6A CN200980114114A CN102015815B CN 102015815 B CN102015815 B CN 102015815B CN 200980114114 A CN200980114114 A CN 200980114114A CN 102015815 B CN102015815 B CN 102015815B
- Authority
- CN
- China
- Prior art keywords
- group
- alcohol
- organic solvent
- aniline point
- polyisocyanates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
- C07C275/58—Y being a hetero atom
- C07C275/60—Y being an oxygen atom, e.g. allophanic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Abstract
Disclosed is a polyisocyanate composition containing a polyisocyanate, which is obtained by reacting hexamethylene diisocyanate and an aliphatic monoalcohol having 11-20 carbon atoms, and a low-polarity organic solvent having an aniline point of 10-70 DEG C or a low-polarity organic solvent having a mixed aniline point of 5-50 DEG C. The polyisocyanate contains an allophanate group, an isocyanurate group and a urethane group in a molecule, and the molar ratio between the allophanate group and the isocyanurate group, namely allophanate group/isocyanurate group, is from 70/30 to 30/70. The composition is soluble in a low-polarity organic solvent, and has excellent compatibility with a polyol compound. Consequently, the composition can provide a coating film having excellent physical properties such as surface hardness.
Description
Technical field
The present invention relates to polyisocyantates composition and use its two-component-type coating composition.
Background technology
To be coating be used to the applications of outdoor base material such as buildings, building structures, the application of the repairing of automobile, plastics etc. due to weathering resistance, filming of wear resistant excellence can be provided to the two-component-type carbamate that the polyisocyanates of usining is used as a kind of composition always.
Because polyisocyanates polarity is high, in this coating, conventionally use the strong solvents such as ester series solvent such as aromatic hydrocarbon solvents, butylacetate such as toluene, dimethylbenzene, that is use the strong solvent of solvency power.
These strong solvents, because smell is large, from improving operating environment, reducing global environment load aspect, have the tendency of avoiding in recent years.Further, application and repair, be coated with while upgrading again on old coating film, repairs with comprising in coating while having high solvent strong solvent, and old coating film swelling or dissolving, may have the necessity that even needs to repair old coating film.Consequently, produce sometimes the problems such as the extension of coating operation and miscellaneousization, the increase of coating expense, claim for eot.
In view of above-mentioned viewpoint, in recent years at a kind of polyisocyanates that is soluble in weakly polar organic solvent of exploitation.
For example, in patent documentation 1 (Japanese kokai publication hei 8-198928 communique), as the polyisocyanates of dilution property excellence in weak polar solvent, disclosing and having made ester ring type vulcabond and dilution property in weak polar solvent is the polyisocyanates that more than 100% polyol reaction obtains.
In addition, in patent documentation 2 (TOHKEMY 2008-24828 communique), as to the solvability of weakly polar organic solvent and with the polyisocyanates of the consistency excellence of silicate compound, the resulting mol ratio of allophanate group/isocyanurate group and the polyisocyanate compound of regulation molecular weight distribution with regulation of monohydroxy-alcohol by aliphatics and/or ester ring type vulcabond and carbon number 1～20 disclosed.
The polyisocyanates of above-mentioned patent documentation 1 and patent documentation 2 is all excellent for weakly polar organic solvent solvability, but aspect the consistency of the polyol compound with host, various physical property such as surface hardness that gained is filmed, has further room for improvement.The leeway that the selection of weak polar solvent is also improved in addition.
Patent documentation 1: Japanese kokai publication hei 8-198928 communique
Patent documentation 2: TOHKEMY 2008-24828 communique
Summary of the invention
the problem that invention will solve
The present invention In view of the foregoing carries out, its object is, a kind of weakly polar organic solvent and excellent with the consistency of polyol compound that dissolves in is provided, can provides with the polyisocyantates composition of filming of the various physical properties excellent headed by surface hardness and use its two-component-type coating composition.
for the scheme of dealing with problems
The inventor is for realizing this object, carried out finding after further investigation repeatedly, for hexamethylene diisocyanate, react with the aliphatic monobasic alcohol of carbon number 11～20 polyisocyanates obtaining, by making the mol ratio of the allophanate group/isocyanurate group of this polyisocyanates, it is specialized range, can improve its solvability to weakly polar organic solvent, and improved by the coating gained that comprises this polyisocyanates and polyvalent alcohol film with the various physical property headed by surface hardness, thereby completed the present invention.
That is, the invention provides:
1. a polyisocyantates composition, it is characterized in that, its comprise make hexamethylene diisocyanate with the aliphatic monobasic alcohol of carbon number 11～20 by reacting the polyisocyanates obtaining, and aniline point is the weakly polar organic solvent that the weakly polar organic solvent of 10～70 ℃ or mixed aniline point are 5～50 ℃; In the molecule of this polyisocyanates, there is allophanate group, isocyanurate group and carbamate groups; And the mol ratio of this allophanate group and isocyanurate group is allophanate group/isocyanurate group=70/30～30/70.
2. according to 1 polyisocyantates composition, wherein, described reaction is to carry out the reaction that allophanic acid esterification reaction is reacted with isocyanuric acid esterification simultaneously.
3. according to 2 polyisocyantates composition, wherein, the catalyzer of described allophanic acid esterification reaction and isocyanuric acid esterification reaction is stannous octoate.
4. a manufacture method for polyisocyanates, is characterized in that, makes hexamethylene diisocyanate and the aliphatic monobasic alcohol of carbon number 11～20 under the existence of stannous octoate catalyzer, carry out that allophanic acid esterification is reacted and isocyanuric acid esterification reaction.
5. a two-component-type coating composition, is characterized in that, comprises the polyisocyantates composition described in any one and polyol compound in 1～3.
the effect of invention
In the present composition, contained polyisocyanates is excellent to the solvability of weakly polar organic solvent (Weak solvent), and the consistency of the fluorine system using with two-component-type coating, acrylic acid series multiple alcohol is good.
The isocyanuric acid ester content of this polyisocyanates is high, therefore, by the solidifying agent using it as two-component-type coating composition, uses, and can improve with the various Physical properties of coating films headed by surface hardness.
In addition, two-component-type coating composition of the present invention, owing to dissolving in weakly polar organic solvent (Weak solvent), therefore, can not corrode bottom when repeating to be coated with, then coating is excellent.
Embodiment
Below, the present invention will be described in more detail for pin.
Polyisocyantates composition of the present invention comprises makes hexamethylene diisocyanate react the weakly polar organic solvent that the polyisocyanates of gained and weakly polar organic solvent that aniline point is 10～70 ℃ or mixed aniline point are 5～50 ℃ with the aliphatic monobasic alcohol of carbon number 11～20; In the molecule of polyisocyanates, there is allophanate group, isocyanurate group and carbamate groups; And the mol ratio of these allophanate group and isocyanurate group meets allophanate group/isocyanurate group=70/30～30/70.
In the present invention, when allophanate group/isocyanurate group (mol ratio) is not during in above-mentioned scope, gained polyisocyanates reduces the solvability of weakly polar organic solvent, and the physical property of filming of using said composition to obtain also reduces.
More preferably allophanate group/isocyanurate group (mol ratio)=60/40～30/70, is further preferably 40/60～30/70.
In addition, the content of carbamate groups is not limited especially, in polyisocyanates of the present invention, with respect to the integral molar quantity of allophanate group and isocyanurate group, the content of carbamate groups is preferably 0.1 % by mole～2 % by mole, more preferably 0.5～2 % by mole.
In addition, the mol ratio of above-mentioned each functional group can be passed through
1h-NMR measures and calculates.
Aliphatic monobasic alcohol as the carbon number 11～20 reacting with hexamethylene diisocyanate, for example can list different tridecanol, 1-undecyl alcohol, 1-lauryl alcohol, 1-eicosanol, 1-heptadecyl alcohol, 1-nonadecanol, 1-tridecanol, 1-tetradecyl alcohol, 1-pentadecanol, stearyl alcohol, isooctadecanol, 3-ethyl-4,5,6-trimethylammonium octanol, 4,5,6,7-tetramethyl-nonyl alcohol, 4,5,8-trimethylammonium decyl alcohol, 4,7,8-trimethylammonium decyl alcohol, 2-hexyl lauryl alcohol, 2-octyl dodecanol, 2-dodecyl decyl alcohol, 2-hexadecyl stearyl alcohol etc.These can be used alone, also two or more use capable of being combined.
In these alcohol, from further raising gained polyisocyantates composition, the solvability of weakly polar organic solvent is considered, be preferably 1-tridecanol, different tridecanol, 1-lauryl alcohol, 1-eicosanol, 1-heptadecyl alcohol, 1-nonadecanol, 1-tetradecyl alcohol, 1-pentadecanol, stearyl alcohol, isooctadecanol, 2-octyl dodecanol, more preferably 1-tridecanol, different tridecanol, 2-octyl dodecanol.
Hexamethylene diisocyanate can be under the existence of organic solvent with reacting of monohydroxy-alcohol or is not existed under organic solvent, be heated to 50～150 ℃ of left and right and carry out.
Allophanic acid esterification can be carried out with urethane simultaneously, also can after urethane, carry out, and be preferably in the present invention after urethane, carries out.When urethane and allophanic acid esterification are carried out simultaneously, under the existence of allophanic acid esterification catalyzer, react, while carrying out allophanate after urethane, there not being the urethane reaction of carrying out the specified time under allophanic acid esterification catalyzer, then add allophanic acid esterification catalyzer and carry out allophanate reaction.
As allophanic acid esterification catalyzer, can from well-known catalysts, suitably select, for example, can use the metal-salt of carboxylic acid.As above-mentioned carboxylic acid, for example can list acetic acid, propionic acid, butyric acid, caproic acid, sad, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, the representative examples of saturated aliphatic carboxylic such as 2 ethyl hexanoic acid, hexahydrobenzoic acid, the saturated monocycle carboxylic acid such as Cyclopentane carboxylic acid, saturated many ring carboxylic acids such as dicyclo (4.4.0) decane-2-carboxylic acid, the mixture of the above-mentioned carboxylic acids such as naphthenic acid (naphthenic acid), oleic acid, linolic acid, linolenic acid, soya fatty acid, the unsaturated aliphatic carboxylic acids such as ready denier oil acid, the aromatic-aliphatic carboxylic acids such as diphenyl acetic acid, M-nitro benzoic acid, the monocarboxylic acid classes such as aromatic carboxylic acid such as toluic acid (toluic acid), phthalic acid, m-phthalic acid, terephthalic acid, naphthalene dicarboxylic acids, succsinic acid, tartrate, oxalic acid, propanedioic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, propene dicarboxylic acid, nonane diacid, sebacic acid, 1,4-cyclohexyl dicarboxylic acid, α-hydrogenation muconic acid, β-hydrogenation muconic acid, α-butyl-α-ethylglutaric acid, α, the polycarboxylic acid classes such as β-diethyl succsinic acid, toxilic acid, fumaric acid, trimellitic acid, pyromellitic acid.
In addition, the metal as forming the metal-salt of carboxylic acid, can list the basic metal such as lithium, sodium, potassium; The alkaline-earth metal such as magnesium, calcium, barium; Other typical metal such as tin, lead; The transition metal such as manganese, iron, cobalt, nickel, copper, zinc, zirconium etc.
Two or more use alone or in combination of these carboxylic metallic salts.In addition, with respect to the total quality of polyisocyanates and alcohol, the consumption of allophanic acid esterification catalyzer is preferably 0.0005～1 quality %, more preferably 0.001～0.1 quality %.
While reacting under the existence of organic solvent, can use the various organic solvents that do not affect reaction, its concrete example can list the aliphatic hydrocarbons such as normal hexane, octane; The alicyclic hydro carbons such as hexanaphthene, methylcyclohexane; The ketones such as acetone, methylethylketone, mibk, pimelinketone; The ester classes such as ritalin, vinyl acetic monomer, N-BUTYL ACETATE, isobutyl acetate; The diol alcohol esters such as ethyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxyl group butylacetic acid ester, ethyl-3-ethoxy-c acid esters; The ethers such as diethyl ether, tetrahydrofuran (THF), diox; The halogenated hydrocarbons such as methyl chloride, methylene dichloride, chloroform, tetracol phenixin, monobromomethane, methylene iodide, ethylene dichloride; N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, hexamethylphosphoramide isopolarity aprotic solvent etc.Two or more use alone or in combination of these solvents.
After reaction finishes, in reaction system, add the reaction terminating agents such as phosphoric acid, phosphoric acid ester, at 30～100 ℃, carry out 1～2 hour termination reaction, stop allophanic acid esterification reaction.
After reaction terminating, by known methods such as thin film distillations, remove unreacted composition, can obtain allophanate-modified polyisocyanates.
The allophanate-modified polyisocyanates of gained (while meeting above-mentioned allophanate group/isocyanurate group scope) can be directly as polyisocyantates composition.
In addition, the allophanate group modified polyisocyanate obtaining as mentioned above mainly has allophanate group, and owing to reacting under the condition in the excessive existence of isocyanate group etc., causes side reaction to occur, and generates isocyanuric acid ester.
Therefore by appropriateness, adjust the various conditions such as ratio of [NCO]/[OH] in allophanic acid esterification, the mol ratio of allophanate group and isocyanurate group in gained polyisocyanates can be adjusted in 70/30～30/70 scope appropriateness.
In addition, can also make the further isocyanuric acid esterification of allophanic acid esterification polyisocyanates by above method, adjust the mol ratio of allophanate group/isocyanurate group.
As isocyanuric acid esterification reaction, can list under the existence of isocyanuric acid esterification catalyzer, make the method for modified polyisocyanate (tripolymer).As such method of modifying, can use the method that for example No. 3371480 communique of Japanese Patent, TOHKEMY 2002-241458 communique are recorded.
As isocyanuric acid esterification catalyzer, can use the phenolates, 2 such as metal-salt such as aliphatic carboxylic acid, potassium phenylate, 4,6-tri-(dimethylaminomethyl) phenol, 2, two (dimethylaminomethyl) phenol, 2 of 4-, 6-bis--tertiary butyl-4-dimethylamino trimethyl silane phenol, triethylamine, N, N ', N " amine compound such as-tri-(dimethylaminopropyl) six hydrogen-s-triazine, diazabicycloundecene.Wherein be preferably the metal-salt of aliphatic carboxylic acid, such as the sodium salt of the carboxylic acids such as preferred acetic acid, propionic acid, undeeanoic acid, caproic acid, sad, tetradecanoic acid, sylvite, pink salt etc.In addition, as commercially available product, also can use 2-hydroxypropyl TMA (TriMethylAmine) octylate (DABCO TMR, Air ProductsJapan K.K. system), potassium octanoate (DABCO K-15, Air Products Japan K.K. system).
As mentioned above, polyisocyanates of the present invention can be manufactured by the method for carrying out the method for allophanic acid esterification and isocyanuric acid esterification or periodically carrying out allophanic acid esterification and isocyanuric acid esterification simultaneously, and in the present invention most preferred method for carry out the method for allophanic acid esterification and isocyanuric acid esterification simultaneously.
Now, as catalyzer, from the viewpoint of being easy to react, control preferred use stannous octoate in above-mentioned various catalyzer.
In addition, polyisocyanates can mix two or more use, now, as long as mixture meets above-mentioned allophanate group and the mol ratio of isocyanurate group, also can use a part not meet the polyisocyanates of the mol ratio of above-mentioned allophanate group and isocyanurate group.
The viscosity of polyisocyanates used in the present invention is also not particularly limited, and is preferably below 2000mPas at 25 ℃, more preferably below 1500mPas, more preferably below 1000mPas.When the viscosity of polyisocyanates exceeds 2000mPas, the viscosity of coating composition uprises, and is sometimes difficult to process.On the other hand, the lower value of viscosity is also not particularly limited, more than being preferably 50mPas from the viewpoint of processing.
Coating composition of the present invention is characterised in that above-mentioned polyisocyanates, therefore, and as react another composition solidifying with it, as long as suitably select from common the used polyol compound of this purposes.
Concrete example can list acrylic acid series multiple alcohol, fluorine is polyvalent alcohol etc., in these, considers weathering resistance, and preferably fluorine is polyvalent alcohol, while considering weathering resistance and cost face balanced, and preferred acrylic acid series multiple alcohol.
In addition, in the present invention, the characteristic from what is called to this above-mentioned polyisocyanates of weakly polar organic solvent favorable solubility, polyol compound preferably dissolves in weakly polar organic solvent.
As dissolving in the acrylic acid series multiple alcohol of weakly polar organic solvent and being not particularly limited, can use known weak solvent soluble acrylic acid series multiple alcohol.As its concrete example, can list ACRYDIC HU-596 (large Japanese ink chemical industry (strain) system), EXXELOR 410 (Asia industry (strain) system), the HITALOID6500 (Hitachi changes into industry (strain) and makes) etc. of commercially available product.
As the fluorine that dissolves in weakly polar organic solvent, be polyvalent alcohol, and be not particularly limited, generally can use known weak solvent soluble fluorine is polyvalent alcohol.Its concrete example can list vinyl fluoride-Vinyl Ether (vinyl acetate) multipolymer etc.Commercially available product can list LumiflonLF800 (Asahi Glass (strain) system) etc.
The hydroxyl value of this polyol compound and acid value are also not particularly limited, and in coating of the present invention, hydroxyl value is preferably 1～300mgKOH/g, more preferably 1～250mgKOH/g.When hydroxyl value is during lower than 1mgKOH/g,, sometimes there is the tendency that the physical property such as coating strength decline in the crosslinked deficiency of filming, while surpassing 300mgKOH/g, film due to become too high and hardening of cross-linking density, servo-actuated property and the flexibility for body material reduces sometimes.
In addition, consider that gained is coated with the treatability of film strength, coating etc., the number-average molecular weight of polyol compound is preferably 5000～20000, and more preferably 7000～15000.Number-average molecular weight is the measured value (polystyrene conversion value) of utilizing gel permeation chromatography (GPC) to measure detecting by differential refractive index meter.
In coating composition of the present invention, the mixing ratio of polyisocyantates composition and polyol compound is that, with respect to 100 mass parts polyvalent alcohols, polyisocyantates composition is preferably 1～150 mass parts, more preferably 1～130 mass parts, more preferably 1～100 mass parts.
For the polyisocyantates composition of coating composition of the present invention, containing aniline point is the weakly polar organic solvent that the weakly polar organic solvent of 10～70 ℃ or mixed aniline point are 5～50 ℃.These weakly polar organic solvents can add in polyisocyanates in advance, also can be before polyisocyanates mix with polyvalent alcohol, and take and adjust viscosity and add in polyisocyanates as object.
In addition, as required, weakly polar organic solvent can add when preparing polyhydric alcohol composition, also can when mixing polyisocyantates composition and polyvalent alcohol, add.
Wherein, " aniline point " is the aniline of capacity and the minimum temperature that sample (organic solvent) exists with homogeneous mixture solotion such as to instigate.In addition, " mixed aniline point " is the minimum temperature of instigating 2 capacity aniline, 1 capacity sample and 1 capacity 1-heptane to exist with homogeneous mixture solotion.The aniline point that aniline point and mixed aniline point can be recorded according to JIS K 2256 and the test method of mixed aniline point are measured.
In addition, the zero pour of aniline is-6 ℃, therefore, at this, below temperature, cannot measure aniline point.Therefore,, in order to measure the solvency power of organic solvent at wide region more, use the mixed aniline point of skellysolve D in aniline.
Above-mentioned aniline point is preferably 10～70 ℃, and more preferably 10～60 ℃, more preferably 10～50 ℃.In addition, during for mixed aniline point, be preferably 5～50 ℃.If aniline point lower than 5 ℃, easily corrodes bottom lower than 10 ℃ or mixed aniline point, if surpassing 70 ℃ or mixed aniline point, aniline point surpasses 50 ℃, not soluble polyisocyanates of the present invention.
As such organic solvent, for example, can list methylcyclohexane (aniline point: 40 ℃), ethylcyclohexane (aniline point: 44 ℃), mineral turpentine (aniline point: 56 ℃), turps (aniline point: 44 ℃), in addition, as the commercially available trade(brand)name of petroleum hydrocarbon, can list High Aromatic White Spirit (HAWS) (Shell ChemicalsJapan system, aniline point: 17 ℃), Low Aromatic White Spirit (LAWS) (Shell Chemicals Japan system, aniline point: 44 ℃), Esso Naphtha No.6 (Exxon Mobile Corporation system, aniline point: 43 ℃), Pegasol 3040 (Exxon Mobile Corporation system, aniline point: 55 ℃), A Solvent (Nippon Oil(Nippon Mitsubishi Oil) society system, aniline point: 45 ℃), Cleansol (Nippon Oil(Nippon Mitsubishi Oil) society system, aniline point: 64 ℃), mineral turpentine A (Nippon Oil(Nippon Mitsubishi Oil) society system, aniline point: 43 ℃), HIAROM 2S (Nippon Oil(Nippon Mitsubishi Oil) society system, aniline point: 44 ℃), Solvesso 100 (Exxon Mobile Corporation system, mixed aniline point: 14 ℃), Solvesso150 (Exxon Mobile Corporation system, mixed aniline point: 18.3 ℃), Swasol100 (Wan Shan petroleum chemistry society system, mixed aniline point: 24.6 ℃), Swasol 200 (Wan Shan petroleum chemistry society system, mixed aniline point: 23.8 ℃), Swasol1000 (Wan Shan petroleum chemistry society system, mixed aniline point: 12.7 ℃), Swasol1500 (Wan Shan petroleum chemistry society system, mixed aniline point: 16.5 ℃), Swasol1800 (Wan Shan petroleum chemistry society system, mixed aniline point: 15.7 ℃), bright dipping IPZOLE 100 (bright dipping Xing Chan society system, mixed aniline point: 13.5 ℃), bright dipping IPZOLE 150 (bright dipping Xing Chan society system, mixed aniline point: 15.2 ℃), Pegasol ARO-80 (Exxon MobileCorporation system, mixed aniline point: 25 ℃), Pegasol R-100 (Exxon MobileCorporation system, mixed aniline point: 14 ℃), the special Hysol (ShellChemicals Japan K.K. system, mixed aniline point: 12.6 ℃) of clear stone, day stone Hysol (Nippon Oil(Nippon Mitsubishi Oil) society system, mixed aniline point: 17 ℃ following) etc.These organic solvents can be used alone a kind, or mix two or more use.
Aniline point is that 10 ℃ of above or mixed aniline points are 5 ℃ of above little features of organic solvent scent of.Therefore,, from environment resistant viewpoint, the coating composition of the present invention that contains such weakly polar organic solvent is also excellent.
In addition, the solvency power of above-mentioned weakly polar organic solvent is low, is difficult for corroding bottom, and therefore, coating composition can repeat coating, is also applicable to repairing coating.
And aforementioned coating composition also can comprise the general various additives for coating.As additive, such as listing softening agent, sanitas, mould inhibitor, algaecide, defoamer, flow agent, pigment dispersing agent, anti-sedimentation agent, anti-sagging agent, catalyzer, curing catalyst, dewatering agent, matting agent, UV light absorber, antioxidant, pigment, tensio-active agent etc.
While being filmed by coating composition making of the present invention, can be applied on the suitable base material such as concrete, mortar, paddle (siding board), extrusion molding plate, ceramic tile, metal, glass, timber, plastics by methods such as brushing, roller coat, sprayings, dry, curing with proper method.
While in addition, carrying out application on dry type building materials, ，Ye Ke factory etc. carries out precoating by flow coating machine or roller coating machine.
In addition, coating composition can directly be coated base material, also can be coated on filler, deposition layer or undercoat (priming paint coating), floating coat (painted etc.).In addition, when base material is metal, also can after the surface treatments such as the processing of enforcement tertiary iron phosphate or zinc phosphate processing, be coated with.
Embodiment
Below list embodiment and comparative example, be described more specifically the present invention, but the invention is not restricted to following embodiment.In addition, with lower, the measured value of viscosity for obtaining by Type B rotational viscosimeter.
[1] manufacture of polyisocyanates
[embodiment 1]
In the four-hole boiling flask of 1 liter of capacity that possesses agitator, thermometer, prolong and nitrogen ingress pipe, drop into hexamethylene diisocyanate (Nippon Polyurethane Industry Co., Ltd.'s system of 880g, NCO content: 49.9 quality %, hereinafter referred to as HDI) and 120g tridecanol (consonance fermentation industry (strain) system), while stirring them, be heated to 85 ℃, carry out urethane reaction in 3 hours.
After this, to the allophanic acid esterification and the isocyanuric acid esterification catalyzer that add 0.1g in this reaction soln, be stannous octoate (Japanese chemical industry (strain) system), at 110 ℃, react to the NCO content that reaches regulation, then adding 0.4g reaction terminating agent is phosphate ester acid (JP-508, north of the city chemical industry (strain) system), at 50 ℃, carry out 1 hour termination reaction.
By this reaction product by thin film distillation (condition: 140 ℃, 0.04kPa) remove excessive HDI, obtain the modified polyisocyanate S-1 of NCO content 15.8 quality %, viscosity (25 ℃) 320mPas, free HDI content 0.1 quality %.
[embodiment 2～4]
Except as shown in table 1 the input amount that changes catalyzer etc., NCO content, with order similarly to Example 1, obtain modified polyisocyanate S-2～S-4.
[embodiment 5]
In the four-hole boiling flask of 1 liter of capacity that possesses agitator, thermometer, prolong and nitrogen ingress pipe, drop into 850g HDI (Nippon Polyurethane Industry Co., Ltd.'s system, 49.9 quality %) and KALCOL 200GD (the 2-octyl dodecanol of 150g NCO content:, flower king (strain) system), stir them on one side, be heated to 85 ℃ on one side, carry out urethane reaction in 3 hours.
After this, to the allophanic acid esterification and the isocyanuric acid esterification catalyzer that add 0.2g in this reaction soln, be stannous octoate (Japanese chemical industry (strain) system), at 110 ℃, react to the NCO content that reaches regulation, then the reaction terminating agent that adds 0.8g is phosphate ester acid (JP-508, north of the city chemical industry (strain) system), at 50 ℃, carry out 1 hour termination reaction.
By this reaction product by thin film distillation (condition: 140 ℃, 0.04kPa) remove excessive HDI, obtain the modified polyisocyanate S-5 of NCO content 15.7 quality %, viscosity (25 ℃) 560mPas, free HDI content 0.2 quality %.
[embodiment 6]
Except as shown in table 1 the input amount that changes catalyzer etc., NCO content, with order similarly to Example 5, obtain modified polyisocyanate S-6.
[comparative example 1]
In the four-hole boiling flask of 1 liter of capacity that possesses agitator, thermometer, prolong and nitrogen ingress pipe, drop into 850g HDI and 150g KALCOL 200GD (2-octyl dodecanol, flower king (strain) system), stir them on one side, be heated to 85 ℃ on one side, carry out urethane reaction in 3 hours.
After this, to the allophanic acid esterification and the isocyanuric acid esterification catalyzer that add 0.4g in this reaction solution, be stannous octoate (Japanese chemical industry (strain) system), at 110 ℃, react to the NCO content that reaches regulation, then the reaction terminating agent that adds 2.0g is phosphate ester acid (JP-508, north of the city chemical industry (strain) system), at 50 ℃, carry out 1 hour termination reaction.
By this reaction product by thin film distillation (condition: 140 ℃, 0.04kPa) remove excessive HDI, obtain the modified polyisocyanate H-1 of NCO content 15.3 quality %, viscosity (25 ℃) 2500mPas, free HDI content 0.1 quality %.
[comparative example 2]
In the four-hole boiling flask of 1 liter of capacity that possesses agitator, thermometer, prolong and nitrogen ingress pipe, drop into 880g HDI and 120g tridecanol (consonance fermentation industry (strain) system), stir them on one side, Yi Bian be heated to 85 ℃, carry out urethane reaction in 3 hours.
After this, to the allophanic acid esterification catalyzer that adds 0.1g in this reaction solution, be zirconium caprylate (first rare element chemistry industry (strain) system), at 110 ℃, react to the NCO content that reaches regulation, then the reaction terminating agent that adds 0.2g is phosphate ester acid (JP-508, north of the city chemical industry (strain) system), at 50 ℃, carry out 1 hour termination reaction.
By this reaction product by thin film distillation (condition: 140 ℃, 0.04kPa) remove excessive HDI, obtain the modified polyisocyanate H-2 of NCO content 14.8 quality %, viscosity (25 ℃) 130mPas, free HDI content 0.1 quality %.
[comparative example 3]
In the four-hole boiling flask of 1 liter of capacity that possesses agitator, thermometer, prolong and nitrogen ingress pipe, drop into 910g HDI, 90g 2-Ethylhexyl Alcohol, be heated to immediately 80 ℃, carry out urethane reaction in 2 hours.
After this, the isocyanuric acid esterification catalyzer that adds 0.1g is 2-hydroxypropyl TMA (TriMethylAmine) octylate (DABCO TMR, Air Products Japan K.K. system), at 80 ℃, react to the NCO content that reaches regulation, then the reaction terminating agent that adds 0.8g is phosphate ester acid (JP-508, north of the city chemical industry (strain) system), at 50 ℃, carry out 1 hour termination reaction.
By this reaction product by thin film distillation (condition: 130 ℃, 0.04kPa) remove excessive HDI, obtain the modified polyisocyanate H-3 of NCO content 19.1 quality %, viscosity (25 ℃) 700mPas, free HDI content 0.2 quality %.
[embodiment 7]
In the four-hole boiling flask of 1 liter of capacity that possesses agitator, thermometer, prolong and nitrogen ingress pipe, drop into the above-mentioned comparative example 2 gained polyisocyanates H-2 of above-described embodiment 4 gained polyisocyanates S-4, the 70g of 130g, carry out 1 hour Agitation and mixing, obtain the modified polyisocyanate S-7 of NCO content 16.0 quality %, viscosity (25 ℃) 240mPas, free HDI content 0.2 quality %.
[comparative example 4]
In the four-hole boiling flask of 1 liter of capacity that possesses agitator, thermometer, prolong and nitrogen ingress pipe, drop into above-described embodiment 4 gained polyisocyanates S-4 of 100g, the above-mentioned comparative example 2 gained polyisocyanates H-2 of 100g, carry out 1 hour Agitation and mixing, obtain the modified polyisocyanate H-4 of NCO content 15.8 quality %, viscosity (25 ℃) 210mPas, free HDI content 0.2 quality %.
For above-described embodiment 1～7 and each polyisocyanates of comparative example 1～4 gained, by following method, measure (generation) mol ratio of allophanate group, isocyanurate group and carbamate groups separately.The results are shown in table 1.
[measuring method]
Use
1h-NMR (Varian Gemini2000 processed (300MHz), near the signal of the hydrogen atom by 8.5ppm and nitrogen atom bonding allophanate group, and near the signal of the hydrogen atom of the methylene radical adjacent with nitrogen-atoms isocyanurate group 3.7ppm, and near the Area Ratio of the signal of 7.0ppm and the hydrogen atom nitrogen atom bonding of carbamate is obtained.Concrete condition determination is as follows.
Measure temperature: 23 ℃
Sample solution concentration: 0.1g/1ml
Cumulative number: 32 times
Relaxation time: 5 seconds
Solvent: deuterated dimethyl sulfoxide
Chemical shift benchmark: the signal of the hydrogen atom of methyl (2.5ppm) in deuterated dimethyl sulfoxide
In addition, for embodiment 1～7 and each polyisocyanates of comparative example 1～4 gained, measure by the following method its to mineral turpentine A (Nippon Oil(Nippon Mitsubishi Oil) (strain) system) solvability at 20 ℃.Result gathers and is shown in table 1.
[measuring method]
Weigh 1g polyisocyanates, add wherein mineral turpentine A, while usining muddiness, as terminal, obtain the now addition of mineral turpentine A (g).
Utilize this addition, by following formula (1), calculate tolerance limit (tolerance).
The aequum of tolerance limit=organic solvent (g)/sample size (1g) (1)
[table 1]
Carbamate ratio: the ratio using the total amount of allophanate group and isocyanurate group as 100 o'clock
[2] manufacture of two-component-type coating composition
[embodiment 8～14, comparative example 5～8]
According to ratio shown in table 2, each polyisocyanates and mineral turpentine A (Nippon Oil(Nippon Mitsubishi Oil) (strain) system) (polyisocyantates composition) and acrylic polyol (the ACRYDIC HU-596 that coordinate embodiment 1～7 and comparative example 1～4 gained, large Japanese ink chemical industry (strain) system), titanium oxide (CR-90, the former industry of stone (strain) is made) and mineral turpentine A (Nippon Oil(Nippon Mitsubishi Oil) (strain) system), prepare two-component-type coating composition.
[table 2]
Utilize applicator that above-described embodiment 8～14 and the prepared two-component-type coating composition of comparative example 6,8 are applied to steel plate (the JIS G3141 trade(brand)name SPCC-SB with methylethylketone degreasing, PF-1077 processes, Nippon Testpanel Co., Ltd system) on, making wet coating thickness is 100 μ m, and slaking 7 days under the environment of 20 ℃ of temperature, relative humidity 65%, what to form dried film thickness be 40～50pm films.For filming of gained, carry out the evaluation of following each characteristic.The results are shown in table 3.
In addition, the prepared two-component-type coating composition of comparative example 5,7, because the tolerance limit to weak polar solvent is not enough, is therefore tested.
(1) resistance to bend(ing)
Whether whether the resistance to bend(ing) test of JI S K-5600-5-1:1999 of take is benchmark, uses the round shape mandrel rod (mandrel) of diameter 2mm, film and break, and from steel plate, peel off when evaluation is crooked along round shape mandrel rod.To film do not occur breaking, unpeeled be judged to be qualified.
(2) resistance to cupping
The resistance to drawing test of JI S K-5600-5-2:1999 of take is benchmark, uses squeezer, and whether whether evaluation filmed and occurred breaking and from steel plate, peeling off when part is out of shape by extruding.Using making by squeezer to film, produce the extruding degree of depth (mm) of breaking, peeling off as resistance to cupping.
(3) resistance to dropping hammer property
Whether whether the resistance to drop weight test of JIS K-5600-5-3:1999 of take is benchmark, uses the hammer of diameter 10.3mm, quality 0.5kg, film and occur breaking, and from steel plate, peel off when evaluation is out of shape by dropping hammer.The minimum height of fall (cm) that the generation of filming is broken, peeled off is as resistance to dropping hammer property.
(4) hardness of film
The scratch hardness test (pencil method) of JIS K-5600-5-4:1999 of take is benchmark, measures the hardness of film coated surface.The hardest pencil hardness that film coated surface is not produced to scratch is as hardness of film.
(5) adaptation
The adaptation of filming is evaluated as follows: take in the checker belt stripping test that JIS K-5600-5-6:1999 is benchmark, the tartan design incision at right angle is filmed, film when being through to bottom and evaluate for the patience of peeling off from bottom (cross-section method).
[table 3]
As shown in Table 3, excellent by the resulting hardness of filming of coating composition of embodiment 8～14, and other each characteristic is also excellent.
Claims (4)
1. a two-component-type coating composition, it comprises polyisocyantates composition and polyol compound, it is characterized in that,
It is the weakly polar organic solvent that the weakly polar organic solvent of 10～70 ℃ or mixed aniline point are 5～50 ℃ that described polyol compound dissolves in aniline point;
Described polyisocyantates composition comprises makes hexamethylene diisocyanate and the aliphatic monobasic alcohol of carbon number 11～20 under the existence of stannous octoate catalyzer, carry out that allophanic acid esterification is reacted and polyisocyanates that isocyanuric acid esterification reaction obtains simultaneously, and aniline point is the weakly polar organic solvent that the weakly polar organic solvent of 10～70 ℃ or mixed aniline point are 5～50 ℃;
In the molecule of described polyisocyanates, there is allophanate group, isocyanurate group and carbamate groups; And,
The mol ratio of described allophanate group and isocyanurate group is allophanate group/isocyanurate group=70/30～30/70,
With respect to the integral molar quantity of allophanate group and isocyanurate group, the content of carbamate groups is 0.1 % by mole～2 % by mole,
The viscosity of described polyisocyantates composition at 25 ℃ is below 2000mPas,
Described aniline point is that weakly polar organic solvent that the weakly polar organic solvent of 10～70 ℃ or mixed aniline point are 5～50 ℃ is to be selected from one kind or two or more in methylcyclohexane, ethylcyclohexane, mineral turpentine, turps or petroleum hydrocarbon.
2. two-component-type coating composition according to claim 1, wherein, the mol ratio of described allophanate group and isocyanurate group is allophanate group/isocyanurate group=69/31～30/70.
3. two-component-type coating composition according to claim 1 and 2, wherein, described aliphatic monobasic alcohol is selected from different tridecanol, 1-undecyl alcohol, 1-lauryl alcohol, 1-eicosanol, 1-heptadecyl alcohol, 1-nonadecanol, 1-tetradecyl alcohol, isooctadecanol, 3-ethyl-4,5,6-trimethylammonium octanol, 4,5,6,7-tetramethyl-nonyl alcohol, 4,5,8-trimethylammonium decyl alcohol, 4,7, one kind or two or more in 8-trimethylammonium decyl alcohol, 2-hexyl lauryl alcohol and 2-octyl dodecanol.
4. in molecule, there is a manufacture method for the polyisocyanates of allophanate group, isocyanurate group and carbamate groups, it is characterized in that,
Make hexamethylene diisocyanate and the aliphatic monobasic alcohol of carbon number 11～20 under the existence of stannous octoate catalyzer, carry out that allophanic acid esterification is reacted and isocyanuric acid esterification reaction obtains polyisocyanates simultaneously,
The allophanate group of described polyisocyanates and the mol ratio of isocyanurate group are allophanate group/isocyanurate group=70/30～30/70,
With respect to the integral molar quantity of allophanate group and isocyanurate group, the content of carbamate groups is 0.1 % by mole～2 % by mole,
Viscosity at 25 ℃ is below 2000mPas.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-114223 | 2008-04-24 | ||
| JP2008114223 | 2008-04-24 | ||
| PCT/JP2009/056041 WO2009130965A1 (en) | 2008-04-24 | 2009-03-26 | Polyisocyanate composition and two-package type coating composition using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102015815A CN102015815A (en) | 2011-04-13 |
| CN102015815B true CN102015815B (en) | 2014-03-05 |
Family
ID=41216704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980114114.6A Active CN102015815B (en) | 2008-04-24 | 2009-03-26 | Polyisocyanate composition and two-package type coating composition using same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5445451B2 (en) |
| CN (1) | CN102015815B (en) |
| TW (1) | TWI481633B (en) |
| WO (1) | WO2009130965A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059215B (en) * | 2013-03-19 | 2016-05-18 | 万华化学（北京）有限公司 | A kind of preparation method of TDI isocyanuric acid ester |
| TWI572633B (en) | 2014-05-02 | 2017-03-01 | Asahi Kasei Chemicals Corp | Polyisocyanate hardening, and polyisocyanate hardening |
| JP6502049B2 (en) * | 2014-09-16 | 2019-04-17 | 旭化成株式会社 | Polyisocyanate composition, coating composition and coating method |
| WO2016098772A1 (en) * | 2014-12-15 | 2016-06-23 | 三井化学株式会社 | Self-repairing polyurethane resin raw material, self-repairing polyurethane resin, self-repairing coating material, self-repairing elastomeric material, self-repairing polyurethane resin raw material production method and self-repairing polyurethane resin production method |
| JP2017082076A (en) * | 2015-10-27 | 2017-05-18 | 旭化成株式会社 | Polyisocyanate composition, paint composition and coating method |
| CN107304244B (en) * | 2016-04-18 | 2020-08-25 | 合肥科天水性科技有限责任公司 | Modified polyisocyanate composition and preparation method thereof |
| KR102050921B1 (en) | 2018-08-02 | 2019-12-03 | 에스케이이노베이션 주식회사 | Organic solvent composition and paint composition comprising the same |
| JP7206089B2 (en) * | 2018-10-04 | 2023-01-17 | 旭化成株式会社 | Polyisocyanate composition, coating composition and coating film |
| JP7361565B2 (en) | 2019-10-24 | 2023-10-16 | Ｄｉｃグラフィックス株式会社 | Liquid printing inks, printed materials, and packaging materials |
| CN116535613A (en) * | 2022-11-16 | 2023-08-04 | 江苏奥斯佳材料科技股份有限公司 | Preparation method of polyurethane curing agent |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5124427A (en) * | 1991-01-22 | 1992-06-23 | Miles Inc. | Polyisocyanates containing allophanate and isocyanurate groups, a process for their production and their use in two-component coating compositions |
| EP0566037A3 (en) * | 1992-04-14 | 1994-02-23 | Takeda Chemical Industries Ltd | |
| JP2003137966A (en) * | 2001-10-31 | 2003-05-14 | Dainippon Ink & Chem Inc | Polyisocyanate curing agent |
| WO2007034883A1 (en) * | 2005-09-22 | 2007-03-29 | Asahi Kasei Chemicals Corporation | Polyisocyanate composition and coating composition containing the same |
| WO2007074831A1 (en) * | 2005-12-28 | 2007-07-05 | Mitsui Chemicals Polyurethanes, Inc. | Method for producing allophanate group-containing polyisocyanate, urethane prepolymer and polyurethane resin composition |
| JP2007269954A (en) * | 2006-03-31 | 2007-10-18 | Asahi Kasei Chemicals Corp | Polyisocyanate composition and two package type polyurethane composition |
| JP2008024828A (en) * | 2006-07-21 | 2008-02-07 | Asahi Kasei Chemicals Corp | Polyisocyanate composition and coating composition |
| WO2008041766A1 (en) * | 2006-10-05 | 2008-04-10 | Mitsui Chemicals Polyurethanes, Inc. | Composition for two-component fluorine coating material |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2610530B2 (en) * | 1988-12-28 | 1997-05-14 | 武田薬品工業株式会社 | Polyisocyanates, their production and use |
| JPH0641270A (en) * | 1992-04-14 | 1994-02-15 | Takeda Chem Ind Ltd | Polyisocyanate containing allophanate nd isocyanurate groups and its production |
| JP3065889B2 (en) * | 1994-06-15 | 2000-07-17 | 旭化成工業株式会社 | Polyisocyanate composition |
| JP4849736B2 (en) * | 2001-05-17 | 2012-01-11 | 旭化成ケミカルズ株式会社 | Method for producing polyisocyanate composition |
| DE60229872D1 (en) * | 2001-09-20 | 2008-12-24 | Asahi Kasei Chemicals Corp | POLYISOCYANATE COMPOSITION WITH ALLOPHANATE GROUP |
| EP1721920B1 (en) * | 2004-03-01 | 2015-05-06 | Asahi Kasei Chemicals Corporation | Blocked polyisocyanate composition and coating composition using same |
| WO2008065732A1 (en) * | 2006-11-27 | 2008-06-05 | Nippon Polyurethane Industry Co., Ltd. | Process for production of modified isocyanate mixture containing allophanate bond and isocyanurate bond |
| JP2009007472A (en) * | 2007-06-28 | 2009-01-15 | Nippon Polyurethane Ind Co Ltd | Resin composition for two-component curable coating material |
-
2009
- 2009-03-26 WO PCT/JP2009/056041 patent/WO2009130965A1/en active Application Filing
- 2009-03-26 CN CN200980114114.6A patent/CN102015815B/en active Active
- 2009-03-26 JP JP2010509119A patent/JP5445451B2/en active Active
- 2009-04-23 TW TW098113499A patent/TWI481633B/en active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5124427A (en) * | 1991-01-22 | 1992-06-23 | Miles Inc. | Polyisocyanates containing allophanate and isocyanurate groups, a process for their production and their use in two-component coating compositions |
| EP0566037A3 (en) * | 1992-04-14 | 1994-02-23 | Takeda Chemical Industries Ltd | |
| JP2003137966A (en) * | 2001-10-31 | 2003-05-14 | Dainippon Ink & Chem Inc | Polyisocyanate curing agent |
| WO2007034883A1 (en) * | 2005-09-22 | 2007-03-29 | Asahi Kasei Chemicals Corporation | Polyisocyanate composition and coating composition containing the same |
| WO2007074831A1 (en) * | 2005-12-28 | 2007-07-05 | Mitsui Chemicals Polyurethanes, Inc. | Method for producing allophanate group-containing polyisocyanate, urethane prepolymer and polyurethane resin composition |
| JP2007269954A (en) * | 2006-03-31 | 2007-10-18 | Asahi Kasei Chemicals Corp | Polyisocyanate composition and two package type polyurethane composition |
| JP2008024828A (en) * | 2006-07-21 | 2008-02-07 | Asahi Kasei Chemicals Corp | Polyisocyanate composition and coating composition |
| WO2008041766A1 (en) * | 2006-10-05 | 2008-04-10 | Mitsui Chemicals Polyurethanes, Inc. | Composition for two-component fluorine coating material |
Non-Patent Citations (1)
| Title |
|---|
| 沈慧芳,涂伟萍,陈焕钦.HDI缩二脲多异氰酸酯的合成.《化工学报》.2001,第52卷(第11期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102015815A (en) | 2011-04-13 |
| JP5445451B2 (en) | 2014-03-19 |
| TW200948837A (en) | 2009-12-01 |
| TWI481633B (en) | 2015-04-21 |
| WO2009130965A1 (en) | 2009-10-29 |
| JPWO2009130965A1 (en) | 2011-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102015815B (en) | Polyisocyanate composition and two-package type coating composition using same | |
| CN101796149B (en) | Coating agent and method for production thereof | |
| CN100450770C (en) | Varnish coated stainless steel plate | |
| CN102307921A (en) | Polyurethane resin aqueous dispersion and manufacturing method thereof | |
| CN102216363A (en) | Polyisocyanate composition and two-pack type coating composition using the same | |
| JP5370736B2 (en) | Curing agent for two-component polyurethane resin paint, method for producing the same, and two-component polyurethane resin paint | |
| JP2017524747A (en) | Silylated polyurethane | |
| CA2307366C (en) | Aqueous two-component polyurethane coating composition with improved adhesion and corrosion resistance | |
| JP6031734B2 (en) | Polyisocyanate composition using allophanate / isocyanurate forming catalyst, method for producing the composition, and two-component coating composition using the composition | |
| CN101657484B (en) | Phosphonate-containing two-component coating system and production and use thereof | |
| KR100446672B1 (en) | New Polyamines and Their Use in Coating Compositions | |
| JP5522506B2 (en) | Curing agent for two-component polyurethane resin paint, method for producing the same, and two-component polyurethane resin paint | |
| US11041043B2 (en) | Polycarbamide resins for metal coating applications | |
| JP5499474B2 (en) | Curing agent composition for two-component curable paint | |
| WO2010024330A1 (en) | Polyisocyanate composition and two-liquid type paint composition utilizing same | |
| TW200932845A (en) | Two-component fluorine-containing coating composition | |
| JP2020196870A (en) | Aqueous two-component type cured resin composition and method for coating article | |
| WO2009119206A1 (en) | Polyisocyanate and two-pack-type coating agent | |
| JP5245741B2 (en) | Polyisocyanate curing agent composition for fluorine-based polyol and two-component coating composition using the same | |
| JP4732615B2 (en) | Coating composition for automobile parts, coating film forming method, and automobile parts | |
| JP2011126945A (en) | Aqueous polyurethane resin composition and aqueous coating composition using the same | |
| KR101310786B1 (en) | The Resin Mixture and Synthetic method of the Resins for high build primer which is applicable on automotive pre-coated coatings | |
| JPH11256102A (en) | Moisture-setting type coating composition | |
| JP2020128503A (en) | Aqueous two component type curable resin composition and article coating method | |
| JP2005054121A (en) | Water-dispersible blocked isocyanate composition, method for producing the same, curing agent for water-based paint using the same and water-based paint composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |